Metal coordination compound, luminescence device and display apparatus

ABSTRACT

An electroluminescence device having a layer containing a specific metal coordination compound is provided. The metal coordination compound is represented by formula (1) below:
 
ML m L′ n   (1),
 
wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L′ are mutually different bidentate ligands; m is 1, 2 or 3 and n is 0, 1 or 2 with the proviso that m+n is 2 or 3; a partial structure MLm is represented by formula (2) shown below and a partial structure ML′ n  is represented by formula (3) or (4) shown below: 
                 
 
The metal coordination compound of the formula (1) is characterized by having at least one aromatic substituent for at least one of CyN1, CyN2, CyC1 and CyC2. The metal coordination compound having the aromatic substituent is effective in providing high-efficiency luminescence, long-term high luminance, and less deterioration by current passing.

FIELD OF THE INVENTION AND RELATED ART

The present invention relates to a luminescence device, a displayapparatus and a metal coordination compound therefor. More specifically,the present invention relates to a luminescence device employing anorganic metal coordination compound having a formula (1) appearinghereinafter as a luminescence material so as to allow stableluminescence efficiency, a display apparatus including the luminescencedevice and the metal coordination compound adapted for use in theluminescence device.

An organic electroluminescence (EL) device has been extensively studiedas a luminescence device with a high responsiveness and high efficiency.

The organic EL device generally has a sectional structure as shown inFIG. 1A or 1B (e.g., as described in “Macromol. Symp.”, 125, pp. 1-48(1997)).

Referring to the figures, the EL device generally has a structureincluding a transparent substrate 15, a transparent electrode 14disposed on the transparent substrate 15, a metal electrode 11 disposedopposite to the transparent electrode 14, and a plurality of organic(compound) layers disposed between the transparent electrode 14 and themetal electrode 11.

Referring to FIG. 1, the EL device in this embodiment has two organiclayers including a luminescence layer 12 and a hole transport layer 13.

The transparent electrode 14 may be formed of a film of ITO (indium tinoxide) having a larger work function to ensure a good hole injectionperformance into the hole transport layer. On the other hand, the metalelectrode 11 may be formed of a layer of aluminum, magnesium, alloysthereof, etc., having a smaller work function to ensure a good electroninjection performance into the organic layer(s).

These (transparent and metal) electrodes 14 and 11 may be formed in athickness of 50-200 nm.

The luminescence layer 12 may be formed of, e.g., aluminum quinolinolcomplex (representative example thereof may include Alq3 describedhereinafter) having an electron transporting characteristic and aluminescent characteristic. The hole transport layer 13 may be formedof, e.g., triphenyldiamine derivative (representative example thereofmay include α-NPD described hereinafter) having an electron donatingcharacteristic.

The above-described EL device exhibits a rectification characteristic,so that when an electric field is applied between the metal electrode 11as a cathode and the transparent electrode 14 as an anode, electrons areinjected from the metal electrode 11 into the luminescence layer 12 andholes are injected from the transparent electrodes 14.

The thus-injected holes and electrons are recombined within theluminescence layer 12 to produce excitons, thus causing luminescence. Atthat time, the hole transport layer 13 functions as an electron-blockinglayer to increase a recombination efficiency at the boundary between theluminescence layer 12 and the hole transport layer 13, thus enhancing aluminescence efficiency.

Referring to FIG. 1B, in addition to the layers shown in FIG. 1A, anelectron transport layer 16 is disposed between the metal electrode 11and the luminescence layer 12, whereby an effective carrier blockingperformance can be ensured by separating functions of luminescence,electron transport and hole transport, thus allowing effectiveluminescence.

The electron transport layer 16 may be formed of, e.g., oxadiazolederivatives.

In ordinary organic EL devices, fluorescence caused during a transitionof luminescent center molecule from a singlet excited state to a groundstate is used as luminescence.

On the other hand, not the above fluorescence (luminescence) via singletexciton, phosphorescence (luminescence) via triplet exciton has beenstudied for use in organic EL device as described in, e.g., “Improvedenergy transfer in electrophosphorescent device” (D. F. O'Brien et al.,Applied Physics Letters, Vol. 74, No. 3, pp. 442-444 (1999)) and “Veryhigh-efficiency green organic light-emitting devices based onelectrophosphorescence” (M. A. Baldo et al., Applied Physics Letters,Vol. 75, No. 1, pp. 4-6 (1999)).

The EL devices shown in these documents may generally have a sectionalstructure shown in FIG. 1C.

Referring to FIG. 1C, four organic layers including a hole transferlayer 13, a luminescence layer 12, an exciton diffusion-prevention layer17, and an electron transport layer 16 are successively formed in thisorder on the transparent electrode (anode) 14.

In the above documents, higher efficiencies have been achieved by usingfour organic layers including a hole transport layer 13 of α-NPD (shownbelow), an electron transport layer 16 of Alq3 (shown below), an excitondiffusion-prevention layer 17 of BPC (shown below), and a luminescencelayer 12 of a mixture of CBP (shown below) as a host material withIr(ppy)₃ (shown below) or PtOEP (shown below) as a guest phosphorescencematerial doped into CBP at a concentration of ca. 6 wt. %.

Alq3: tris(8-hydroxyquinoline) aluminum (aluminum-quinolinol complex),

α-NPD: N4,N4′-di-naphthalene-1-yl-N4,N4′-diphenyl-biphenyl-4,4′-diamine(4,4′-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl),

CBP: 4,4′-N,N′-dicarbazole-biphenyl,

BCP: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline,

Ir(ppy)₃: fac tris(2-phenylpyridine)iridium (iridium-phenylpyridinecomplex), and

PtEOP: 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine platinum(platinum-octaethyl porphine complex).

The phosphorescence (luminescence) material used in the luminescencelayer 12 has attracted notice. This is because the phosphorescencematerial is expected to provide a higher luminescence efficiency inprinciple.

More specifically, in the case of the phosphorescence material, excitonsproduced by recombination of carriers comprise singlet excitons andtriplet excitons presented in a ratio of 1:3. For this reason, whenfluorescence caused during the transition from the singlet excited stateto the ground state is utilized, a resultant luminescence efficiency is25% (as upper limit) based on all the produced excitons in principle.

On the other hand, in the case of utilizing phosphorescence causedduring transition from the triplet excited state, a resultantluminescence efficiency is expected to be at least three times that ofthe case of fluorescence in principle. In addition thereto, ifintersystem crossing from the singlet excited state (higher energylevel) to the triplet excited state is taken into consideration, theluminescence efficiency of phosphorescence can be expected to be 100%(four times that of fluorescence) in principle.

The use of phosphorescence based on transition from the triplet excitedstate has also been proposed in, e.g., Japanese Laid-Open PatentApplication (JP-A) 11-329739, JP-A 11-256148 and JP-A 8-319482.

However, the above-mentioned organic EL devices utilizingphosphorescence have accompanied with a problem of luminescentdeterioration particularly in an energized state.

The reason for luminescent deterioration has not been clarified as yetbut may be attributable to such a phenomenon that the life of tripletexciton is generally longer than that of singlet exciton by at leastthree digits, so that molecule is placed in a higher-energy state for along period to cause reaction with ambient substance, formation ofexciplex or excimer, change in minute molecular structure, structuralchange of ambient substance, etc.

Accordingly, the (electro)phosphorescence EL device is expected toprovide a higher luminescence efficiency as described above, while theEL device is required to suppress or minimize the luminescentdeterioration in energized state. Further, a luminescence centermaterial for the EL device is required to allow high-efficiencyluminescence and exhibit a good stability.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a luminescence devicecapable of providing a high-efficiency luminescent state at a highbrightness (or luminance) for a long period while minimizing thedeterioration in luminescence in energized state.

Another object of the present invention is to provide a displayapparatus including the luminescence device.

A further object of the present invention is to provide a metalcoordination compound as a luminescence center material suitable for anorganic layer for the luminescence device.

According to the present invention, there is provided a metalcoordination compound (metal complex), particularly an iridium complex,characterized by having at least one aromatic substituent. Morespecifically, there is provided a metal coordination compoundrepresented by formula (1) below:ML_(m)L′_(n)  (1),wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L′ are mutuallydifferent bidentate ligands; m is 1, 2 or 3 and n is 0, 1 or 2 with theproviso that m+n is 2 or 3; a partial structure MLm is represented byformula (2) shown below and a partial structure ML′_(n) is representedby formula (3) or (4) shown below:

wherein CyN1 and CyN2 are each cyclic group capable of having asubstituent, including a nitrogen atom and bonded to the metal atom Mvia the nitrogen atom; CyC1 and CyC2 are each cyclic group capable ofhaving a substituent, including a carbon atom and bonded to the metalatom M via the carbon atom with the proviso that the cyclic group CyN1and the cyclic group CyC1 are bonded to each other via a covalent bondand the cyclic group CyN2 and the cyclic group CyC2 are bonded to eachother via a covalent bond;

the optional substituent of the cyclic groups is selected from a halogenatom, cyano group, a nitro group, a trialkylsilyl group of which thealkyl groups are independently a linear or branched alkyl group having 1to 8 carbon atoms, a linear or branched alkyl group having 1 to 20carbon atoms of which the alkyl group can include one or non-neighboringtwo or more methylene groups that can be replaced with —O—, —S—, —CO—,—CO—O—, —O—CO—, —CH═CH— or —C≡C—, and the alkyl group can include ahydrogen atom that can be optionally replaced with a fluorine atom; oran aromatic group capable of having a substituent which is selected froman aromatic group capable of having a substituent (that is a halogenatom, a cyano atom, a nitro atom, a linear or branched alkyl grouphaving 1 to 20 carbon atoms of which the alkyl group can include one ornon-neighboring two or more methylene groups that can be replaced with—O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C—, and the alkyl groupcan include a hydrogen atom that can be optionally replaced with afluorine atom), a halogen atom, a cyano atom, a nitro atom, and a linearor branched alkyl group having 1 to 20 carbon atoms (of which the alkylgroup can include one or non-neighboring two or more methylene groupsthat can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or—C≡C—, and the alkyl group can include a hydrogen atom that can beoptionally replaced with a fluorine atom);

E and G are independently a linear or branched alkyl group having 1 to20 carbon atoms of which the alkyl group can include a hydrogen atomthat can be optionally replaced with a fluorine atom, or an aromaticgroup capable of having a substituent (that is a halogen atom, a cyanoatom, a nitro atom, a trialkylsilyl group of which the alkyl groups areindependently a linear or branched alkyl group having 1-8 carbon atoms,a linear or branched alkyl group having 1 to 20 carbon atoms of whichthe alkyl group can include one or non-neighboring two or more methylenegroups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH—or —C≡C—, and the alkyl group can include a hydrogen atom that can beoptionally replaced with a fluorine atom; and

the cyclic groups CyN1, CyN2, CyC1 and CyC2 have at least one aromaticsubstituent capable of having a substituent which is selected from anaromatic group capable of having a substituent (that is a halogen atom,a cyano atom, a nitro atom, a linear or branched alkyl group having 1 to20 carbon atoms of which the alkyl group can include one ornon-neighboring two or more methylene groups that can be replaced with—O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C—C—, and the alkyl groupcan include a hydrogen atom that can be optionally replaced with afluorine atom), a halogen atom, a cyano atom, a nitro atom, a linear orbranched alkyl group having 1 to 20 carbon atoms of which the alkylgroup can include one or non-neighboring two or more methylene groupsthat can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or—C≡C—, and the alkyl group can include a hydrogen atom that can beoptionally replaced with a fluorine atom).

In the formula (1), M may preferably be Ir as described above, and n maypreferably be 0.

In the formula (2), CyN1 and CyC1 may preferably be any one of thefollowing combinations:

CyN1 CyC1 pyridyl naphthyl pyridyl thienyl pyridyl benzothienyl

The present invention also provides an electroluminescence device,comprising: a pair of electrodes disposed on a substrate, and aluminescence unit comprising at least one organic compound disposedbetween the electrodes, wherein the organic compound comprises a metalcoordination compound represented by the above-mentioned formula (1).

In the electroluminescence device, a voltage is applied between theelectrodes to emit light.

In a preferred embodiment of the electroluminescence device, a voltageis applied between the electrodes to emit phosphorescence.

The present invention further provides a picture display apparatus,comprising an electroluminescence device described above and a means forsupplying electric signals to the electroluminescence device.

These and other objects, features and advantages of the presentinvention will become more apparent upon a consideration of thefollowing description of the preferred embodiments of the presentinvention taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A, 1B and 1C illustrate embodiments of the luminescence deviceaccording to the present invention, respectively.

FIG. 2 schematically illustrates a panel structure including an ELdevice and drive means.

FIGS. 3A, 3B and 3C show device performances of a luminescence deviceused in Example 9 appearing hereinafter, wherein FIG. 3A shows anelectric field strength-current density curve, FIG. 3B shows an electricfield strength-luminance curve, and FIG. 3C shows a luminescencespectrum under application of a voltage of 10 volts.

DETAILED DESCRIPTION OF THE INVENTION

In the case where the luminescence layer comprises a host materialhaving a carrier-transporting function and a phosphorescent guestmaterial, a process of phosphorescence via triplet excitons may includeunit processes as follows:

-   1. transportation of electrons and holes within a luminescence    layer,-   2. formation of host excitons,-   3. excitation energy transfer between host molecules,-   4. excitation energy transfer from the host to the guest,-   5. formation of guest triplet excitons, and-   6. transition of the guest triplet excitons to the ground state and    phosphorescence.

Desirable energy transfer in each unit process and luminescence arecaused in competition with various energy deactivation processes.

Needless to say, a luminescence efficiency of an organic luminescencedevice is increased by increasing the luminescence quantum yield of aluminescence center material. In addition thereto, an efficient energytransfer between host material molecules and/or between host materialmolecule and guest material molecule is also an important factor.

Further, the above-described luminescent deterioration in energizedstate may presumably relate to the luminescent center material per se oran environmental change thereof by its ambient molecular structure.

For this reason, our research group has extensively investigated aneffect of use of the metal coordination compound of formula (1) as theluminescent center material and as a result, has found that the metalcoordination compound of formula (1) allows a high-efficiencyluminescence with a high brightness (luminance) for a long period, andless deterioration in energized state.

The metal coordination compound represented by the above formula (1)according to the present invention causes phosphorescence (luminescence)and its lowest excited state is believed to be an MLCT* (metal-to-ligandcharge transfer) excited state or π-π* excited state in a triplet state.The phosphorescent emission of light (phosphorescence) is caused at thetime of transition from such a state to the ground state.

The metal coordination compound of formula (1) according to the presentinvention has been found to provide a higher phosphorescence (quantum)yield of 0.05-0.9 and a shorter phosphorescence life of 1-40 μsec, as aresult of our luminescence experiment based on photoluminescence byphoto-excitation.

The shorter phosphorescence life is necessary to provide a resultant ELdevice with a higher luminescence efficiency. This is because the longerphosphorescence life increases molecules placed in their triplet excitedstate which is a waiting state for phosphorescence, thus lowering theresultant luminescence efficiency particularly at a higher currentdensity. Further, an emission wavelength can be controlled by changingappropriately substituents R1 to T6 and species of aromatic group of themetal coordination compound of the formula (1).

Also from these viewpoints, the metal coordination compound of formula(1) according to the present invention is a suitable luminescentmaterial for an EL device with a higher phosphorescence yield and ashorter phosphorescence life.

Particularly, by providing an aromatic group as a substituent (i.e.,aromatic substituent) of the metal coordination compound of the formula(1), the resultant substituent has π-electron system extended to theoutside of the metal coordination compound molecules, thus facilitatingenergy transfer from a host material and assisting electron/holetransport functions to result in an improved carrier transportperformance. Further, in the present invention, the metal coordinationcompound of the formula (1) may preferably have the cyclic group CyN1and/or CyN2 having pyridine structure, a pyridine derivative whereon oneof CH groups is substituted with N atom, and five-membered ringstructures containing nitrogen atom and/or sulfur atom. By these partialstructures, the resultant metal coordination compound of the formula (1)can be synthesized with a high yield and an excellent stabilitynecessary for the luminescence material.

In addition, as substantiated in Examples appearing hereinafter, it hasbeen confirmed that the metal coordination compound of the formula (1)also exhibited an excellent stability in a durability test by continuouscurrent passage. This may be attributable to a controlled intermolecularinteraction of the metal coordination compound of the formula (1) withthe host material by introducing the aromatic substituent characterizingthe metal coordination compound of the present invention into the metalcoordination compound thereby to change an intermolecular interaction.As a result, it becomes possible to suppress formation of excitonassociates leading to thermal deactivation, thus also reducing quenchingprocess to improve phosphorescence yield and device characteristics.

In the present invention, as the aromatic substituent for the metalcoordination compound of the formula (1), it is preferred to use anaromatic group selected from the group consisting of those (sPh to sPe)shown hereinafter.

In the present invention, the luminescence device may preferably includethe organic layer comprising the above-mentioned metal coordinationcompound between a pair of oppositely disposed electrodes comprising atransparent electrode (anode) and a metal electrode (cathode) which aresupplied with a voltage to cause luminescence, thus constituting anelectric-field luminescence device.

The luminescence device of the present invention has a layer structureshown in FIGS. 1A to 1C as specifically described above.

By the use of the metal coordination compound of formula (1) of thepresent invention, the resultant luminescence device has a highluminescence efficiency as described above.

The luminescence device according to the present invention may beapplicable to devices required to allow energy saving and highluminance, such as those for display apparatus and illuminationapparatus, a light source for printers, and backlight (unit) for aliquid crystal display apparatus. Specifically, in the case of using theluminescence device of the present invention in the display apparatus,it is possible to provide a flat panel display apparatus capable ofexhibiting an excellent energy saving performance, a high visibility anda good lightweight property. With respect to the light source, itbecomes possible to replace a laser light source of laser beam printercurrently used widely with the luminescence device according to thepresent invention. Further, when the luminescence device of the presentinvention is arranged in independently addressable arrays as an exposuremeans for effecting desired exposure of light to a photosensitive drumfor forming an image, it becomes possible to considerably reducing thevolume (size) of image forming apparatus. With respect to theillumination apparatus and backlight (unit), the resultant apparatus(unit) using the luminescence device of the present invention isexpected to have an energy saving effect.

For the application to a display, a drive system using a thin-filmtransistor (TFT) drive circuit according to an active matrix-scheme maybe used. Hereinbelow, an embodiment of using a device of the presentinvention in combination with an active matrix substrate is brieflydescribed with reference to FIG. 2.

FIG. 2 illustrates an embodiment of panel structure comprising an ELdevice and drive means. The panel is provided with a scanning signaldriver, a data signal driver and a current supply source which areconnected to gate selection lines, data signal lines and current supplylines, respectively. At each intersection of the gate selection linesand the data signal lines, a display pixel electrode is disposed. Thescanning signal drive sequentially selects the gate selection lines G1,G2, G3 . . . Gn, and in synchronism herewith, picture signals aresupplied from the data signal driver to display a picture (image).

By driving a display panel including a luminescence layer comprising aluminescence material of the present invention, it becomes possible toprovide a display which exhibits a good picture quality and is stableeven for a long period display.

Some synthetic paths for providing a metal coordination compoundrepresented by the above-mentioned formula (1) are illustrated belowwith reference to an iridium coordination compound (m+n=3) for example:

Other metal coordination compound (M=Pt, Rh and Pd) can also besynthesized in a similar manner.

Some specific structural examples of metal coordination compounds usedin the present invention are shown in Tables 1 to Tables 17 appearinghereinafter, which are however only representative examples and are notexhaustive. Ph to sPe for CyN1, CyN2, CyC1, CyC2 and aromaticsubstituent(s) shown in Tables 1 to 17 represent partial structuresshown below.

TABLE 1 No M m CyN1 CyC1 R1 R2 R3 R4 1 Ir 3 Pr Ph H H sPh H 2 Ir 3 Pr PhH H sNp1 H 3 Ir 3 Pr Ph H H sNp2 H 4 Ir 3 Pr Ph H H sTn1 H 5 Ir 3 Pr PhH H sTn3 H 6 Ir 3 Pr Ph H H sPr H 7 Ir 3 Pr Ph H H sPe H 8 Ir 3 Pr Tn1 HH sPh H 9 Ir 3 Pr Tn1 H H sNp1 H 10 Ir 3 Pr Tn1 H H sNp2 H 11 Ir 3 PrTn1 H H sTn1 H 12 Ir 3 Pr Tn1 H H sTn3 H 13 Ir 3 Pr Tn1 H H sPr H 14 Ir3 Pr Tn1 H H sPe H 15 Ir 3 Pr Tn2 H H sPh H 16 Ir 3 Pr Tn2 H H sNp1 H 17Ir 3 Pr Tn2 H H sNp2 H 18 Ir 3 Pr Tn2 H H sTn1 H 19 Ir 3 Pr Tn2 H H sTn3H 20 Ir 3 Pr Tn2 H H sPr H 21 Ir 3 Pr Tn2 H H sPe H 22 Ir 3 Pr Tn3 H HsPh H 23 Ir 3 Pr Tn3 H H sNp1 H 24 Ir 3 Pr Tn3 H H sNp2 H 25 Ir 3 Pr Tn3H H sTn1 H 26 Ir 3 Pr Tn3 H H sTn3 H 27 Ir 3 Pr Tn3 H H sPr H 28 Ir 3 PrTn3 H H sPe H 29 Ir 3 Pr Tn4 H H sPh H 30 Ir 3 Pr Tn4 H H sNp1 H 31 Ir 3Pr Tn4 H H sNp2 H 32 Ir 3 Pr Tn4 H H sTn1 H 33 Ir 3 Pr Tn4 H H sTn3 H 34Ir 3 Pr Tn4 H H sPr H 35 Ir 3 Pr Tn4 H H sPe H 36 Ir 3 Pr Np1 H H sPh H37 Ir 3 Pr Np1 H H sNp1 H 38 Ir 3 Pr Np1 H H sNp2 H 39 Ir 3 Pr Np1 H HsTn1 H 40 Ir 3 Pr Np1 H H sTn3 H 41 Ir 3 Pr Np1 H H sPr H 42 Ir 3 Pr Np1H H sPe H 43 Ir 3 Pr Np2 H H H sPh 44 Ir 3 Pr Np2 H H sNp1 H 45 Ir 3 PrNp2 H H sNp2 H 46 Ir 3 Pr Np2 H H sTn1 H 47 Ir 3 Pr Np2 H H sTn3 H 48 Ir3 Pr Np2 H H sPr H 49 Ir 3 Pr Np2 H H sPe H 50 Ir 3 Pr Pe H H sPh H 51Ir 3 Pr Pe H H sNp1 H 52 Ir 3 Pr Pe H H sNp2 H

TABLE 2 No M m CyN1 CyC1 R1 R2 R3 R4 53 Ir 3 Pr Pe H H sTn1 H 54 Ir 3 PrPe H H sTn3 H 55 Ir 3 Pr Pe H H sPr H 56 Ir 3 Pr Pe H H sPe H 57 Ir 3 PrCn1 H H sPh H 58 Ir 3 Pr Cn1 H H sNp1 H 59 Ir 3 Pr Cn1 H H sNp2 H 60 Ir3 Pr Cn1 H H sTn1 H 61 Ir 3 Pr Cn1 H H sTn3 H 62 Ir 3 Pr Cn1 H H sPr H63 Ir 3 Pr Cn1 H H sPe H 64 Ir 3 Pr Cn2 H H sPh H 65 Ir 3 Pr Cn2 H HsNp1 H 66 Ir 3 Pr Cn2 H H sNp2 H 67 Ir 3 Pr Cn2 H H sTn1 H 68 Ir 3 PrCn2 H H sTn3 H 69 Ir 3 Pr Cn2 H H sPr H 70 Ir 3 Pr Cn2 H H sPe H 71 Ir 3Pr Cz H H sPh H 72 Ir 3 Pr Cz H H sNp1 H 73 Ir 3 Pr Cz H H sNp2 H 74 Ir3 Pr Cz H H sTn1 H 75 Ir 3 Pr Cz H H sTn3 H 76 Ir 3 Pr Cz H H sPr H 77Ir 3 Pr Cz H H sPe H 78 Ir 3 Pd Ph H H sPh H 79 Ir 3 Pd Ph H H sNp1 H 80Ir 3 Pd Ph H H sNp2 H 81 Ir 3 Pd Ph H H sTn1 H 82 Ir 3 Pd Ph H H sTn3 H83 Ir 3 Pd Ph H H sPr H 84 Ir 3 Pd Ph H H sPe H 85 Ir 3 Pd Tn1 H H sPh H86 Ir 3 Pd Tn1 H H sNp1 H 87 Ir 3 Pd Tn1 H H sNp2 H 88 Ir 3 Pd Tn1 H HsTn1 H 89 Ir 3 Pd Tn1 H H sTn3 H 90 Ir 3 Pd Tn1 H H sPr H 91 Ir 3 Pd Tn1H H sPe H 92 Ir 3 Pd Tn2 H H sPh H 93 Ir 3 Pd Tn2 H H sNp1 H 94 Ir 3 PdTn2 H H sNp2 H 95 Ir 3 Pd Tn2 H H sTn1 H 96 Ir 3 Pd Tn2 H H sTn3 H 97 Ir3 Pd Tn2 H H sPr H 98 Ir 3 Pd Tn2 H H sPe H 99 Ir 3 Pd Tn3 H H sPh H 100Ir 3 Pd Tn3 H H sNp1 H 101 Ir 3 Pd Tn3 H H sNp2 H 102 Ir 3 Pd Tn3 H HsTn1 H 103 Ir 3 Pd Tn3 H H sTn3 H 104 Ir 3 Pd Tn3 H H sPr H

TABLE 3 No M m CyN1 CyC1 R1 R2 R3 R4 105 Ir 3 Pd Tn3 H H sPe H 106 Ir 3Pd Tn4 H H sPh H 107 Ir 3 Pd Tn4 H H sNp1 H 108 Ir 3 Pd Tn4 H H sNp2 H109 Ir 3 Pd Tn4 H H sTn1 H 110 Ir 3 Pd Tn4 H H sTn3 H 111 Ir 3 Pd Tn4 HH sPr H 112 Ir 3 Pd Tn4 H H sPe H 113 Ir 3 Pd Np1 H H sPh H 114 Ir 3 PdNp1 H H sNp1 H 115 Ir 3 Pd Np1 H H sNp2 H 116 Ir 3 Pd Np1 H H sTn1 H 117Ir 3 Pd Np1 H H sTn3 H 118 Ir 3 Pd Np1 H H sPr H 119 Ir 3 Pd Np1 H H sPeH 120 Ir 3 Pd Np2 H H sPh H 121 Ir 3 Pd Np2 H H sNp1 H 122 Ir 3 Pd Np2 HH sNp2 H 123 Ir 3 Pd Np2 H H sTn1 H 124 Ir 3 Pd Np2 H H sTn3 H 125 Ir 3Pd Np2 H H sPr H 126 Ir 3 Pd Np2 H H sPe H 127 Ir 3 Pd Pe H H sPh H 128Ir 3 Pd Pe H H sNp1 H 129 Ir 3 Pd Pe H H sNp2 H 130 Ir 3 Pd Pe H H sTn1H 131 Ir 3 Pd Pe H H sTn3 H 132 Ir 3 Pd Pe H H sPr H 133 Ir 3 Pd Pe H HsPe H 134 Ir 3 Pd Cn1 H H sPh H 135 Ir 3 Pd Cn1 H H sNp1 H 136 Ir 3 PdCn1 H H sNp2 H 137 Ir 3 Pd Cn1 H H sTn1 H 138 Ir 3 Pd Cn1 H H sTn3 H 139Ir 3 Pd Cn1 H H sPr H 140 Ir 3 Pd Cn1 H H sPe H 141 Ir 3 Pd Cn2 H H sPhH 142 Ir 3 Pd Cn2 H H sNp1 H 143 Ir 3 Pd Cn2 H H sNp2 H 144 Ir 3 Pd Cn2H H sTn1 H 145 Ir 3 Pd Cn2 H H sTn3 H 146 Ir 3 Pd Cn2 H H sPr H 147 Ir 3Pd Cn2 H H sPe H 148 Ir 3 Pd Cz H H sPh H 149 Ir 3 Pd Cz H H sNp1 H 150Ir 3 Pd Cz H H sNp2 H 151 Ir 3 Pd Cz H H sTn1 H 152 Ir 3 Pd Cz H H sTn3H 153 Ir 3 Pd Cz H H sPr H 154 Ir 3 Pd Cz H H sPe H 155 Ir 3 Pz Ph H HsPh H 156 Ir 3 Pd Ph H H sNp1 H

TABLE 4 No M m CyN1 CyC1 R1 R2 R3 R4 157 Ir 3 Pd Ph H H sNp2 H 158 Ir 3Pd Ph H H sTn1 H 159 Ir 3 Pd Ph H H sTn3 H 160 Ir 3 Pd Ph H H sPr H 161Ir 3 Pd Ph H H sPe H 162 Ir 3 Pd Tn1 H H sPh H 163 Ir 3 Pd Tn1 H H sNp1H 164 Ir 3 Pd Tn1 H H sNp2 H 165 Ir 3 Pd Tn1 H H sTn1 H 166 Ir 3 Pd Tn1H H sTn3 H 167 Ir 3 Pd Tn1 H H sPr H 168 Ir 3 Pd Tn1 H H sPe H 169 Ir 3Pd Tn2 H H sPh H 170 Ir 3 Pd Tn2 H H sNp1 H 171 Ir 3 Pd Tn2 H H sNp2 H172 Ir 3 Pd Tn2 H H sTn1 H 173 Ir 3 Pd Tn2 H H sTn3 H 174 Ir 3 Pd Tn2 HH sPr H 175 Ir 3 Pd Tn2 H H sPe H 176 Ir 3 Pd Tn3 H H sPh H 177 Ir 3 PdTn3 H H sNp1 H 178 Ir 3 Pd Tn3 H H sNp2 H 179 Ir 3 Pd Tn3 H H sTn1 H 180Ir 3 Pd Tn3 H H sTn3 H 181 Ir 3 Pd Tn3 H H sPr H 182 Ir 3 Pd Tn3 H H sPeH 183 Ir 3 Pd Tn4 H H sPh H 184 Ir 3 Pd Tn4 H H sNp1 H 185 Ir 3 Pd Tn4 HH sNp2 H 186 Ir 3 Pd Tn4 H H sTn1 H 187 Ir 3 Pd Tn4 H H sTn3 H 188 Ir 3Pd Tn4 H H sPr H 189 Ir 3 Pd Tn4 H H sPe H 190 Ir 3 Pd Np1 H H sPh H 191Ir 3 Pd Np1 H H sNp1 H 192 Ir 3 Pd Np1 H H sNp2 H 193 Ir 3 Pd Np1 H HsTn1 H 194 Ir 3 Pd Np1 H H sTn3 H 195 Ir 3 Pd Np1 H H sPr H 196 Ir 3 PdNp1 H H sPe H 197 Ir 3 Pd Np2 H H sPh H 198 Ir 3 Pd Np2 H H sNp1 H 199Ir 3 Pd Np2 H H sNp2 H 200 Ir 3 Pd Np2 H H sTn1 H 201 Ir 3 Pd Np2 H HsTn3 H 202 Ir 3 Pd Np2 H H sPr H 203 Ir 3 Pd Np2 H H sPe H 204 Ir 3 PdPe H H sPh H 205 Ir 3 Pd Pe H H sNp1 H 206 Ir 3 Pd Pe H H sNp2 H 207 Ir3 Pd Pe H H sTn1 H 208 Ir 3 Pd Pe H H sTn3 H

TABLE 5 No M m CyN1 CyC1 R1 R2 R3 R4 209 Ir 3 Pd Pe H H sPr H 210 Ir 3Pd Pe H H sPe H 211 Ir 3 Pd Cn1 H H sPh H 212 Ir 3 Pd Cn1 H H sNp1 H 213Ir 3 Pd Cn1 H H sNp2 H 214 Ir 3 Pd Cn1 H H sTn1 H 215 Ir 3 Pd Cn1 H HsTn3 H 216 Ir 3 Pd Cn1 H H sPr H 217 Ir 3 Pd Cn1 H H sPe H 218 Ir 3 PdCn2 H H sPh H 219 Ir 3 Pd Cn2 H H sNp1 H 220 Ir 3 Pd Cn2 H H sNp2 H 221Ir 3 Pd Cn2 H H sTn1 H 222 Ir 3 Pd Cn2 H H sTn3 H 223 Ir 3 Pd Cn2 H HsPr H 224 Ir 3 Pd Cn2 H H sPe H 225 Ir 3 Pd Cz H H sPh H 226 Ir 3 Pd CzH H sNp1 H 227 Ir 3 Pd Cz H H sNp2 H 228 Ir 3 Pd Cz H H sTn1 H 229 Ir 3Pd Cz H H sTn3 H 230 Ir 3 Pd Cz H H sPr H 231 Ir 3 Pd Cz H H sPe H 232Ir 3 Pz Ph H H sPh H 233 Ir 3 Pz Ph H H sNp1 H 234 Ir 3 Pz Ph H H sNp2 H235 Ir 3 Pz Ph H H sTn1 H 236 Ir 3 Pz Ph H H sTn3 H 237 Ir 3 Pz Ph H HsPr H 238 Ir 3 Pz Ph H H sPe H 239 Ir 3 Pz Tn1 H H sPh H 240 Ir 3 Pz Tn1H H sNp1 H 241 Ir 3 Pz Tn1 H H sNp2 H 242 Ir 3 Pz Tn1 H H sTn1 H 243 Ir3 Pz Tn1 H H sTn3 H 244 Ir 3 Pz Tn1 H H sPr H 245 Ir 3 Pz Tn1 H H sPe H246 Ir 3 Pz Tn2 H H sPh H 247 Ir 3 Pz Tn2 H H sNp1 H 248 Ir 3 Pz Tn2 H HsNp2 H 249 Ir 3 Pz Tn2 H H sTn1 H 250 Ir 3 Pz Tn2 H H sTn3 H 251 Ir 3 PzTn2 H H sPr H 252 Ir 3 Pz Tn2 H H sPe H 253 Ir 3 Pz Tn3 H H sPh H 254 Ir3 Pz Tn3 H H sNp1 H 255 Ir 3 Pz Tn3 H H sNp2 H 256 Ir 3 Pz Tn3 H H sTn1H 257 Ir 3 Pz Tn3 H H sTn3 H 258 Ir 3 Pz Tn3 H H sPr H 259 Ir 3 Pz Tn3 HH sPe H 260 Ir 3 Pz Tn4 H H sPh H

TABLE 6 No M m CyN1 CyC1 R1 R2 R3 R4 261 Ir 3 Pz Tn4 H H sNp1 H 262 Ir 3Pz Tn4 H H sNp2 H 263 Ir 3 Pz Tn4 H H sTn1 H 264 Ir 3 Pz Tn4 H H sTn3 H265 Ir 3 Pz Tn4 H H sPr H 266 Ir 3 Pz Tn4 H H sPe H 267 Ir 3 Pz Np1 H HsPh H 268 Ir 3 Pz Np1 H H sNp1 H 269 Ir 3 Pz Np1 H H sNp2 H 270 Ir 3 PzNp1 H H sTn1 H 271 Ir 3 Pz Np1 H H sTn3 H 272 Ir 3 Pz Np1 H H sPr H 273Ir 3 Pz Np1 H H sPe H 274 Ir 3 Pz Np2 H H sPh H 275 Ir 3 Pz Np2 H H sNp1H 276 Ir 3 Pz Np2 H H sNp2 H 277 Ir 3 Pz Np2 H H sTn1 H 278 Ir 3 Pz Np2H H sTn3 H 279 Ir 3 Pz Np2 H H sPr H 280 Ir 3 Pz Np2 H H sPe H 281 Ir 3Pz Pe H H sPh H 282 Ir 3 Pz Pe H H sNp1 H 283 Ir 3 Pz Pe H H sNp2 H 284Ir 3 Pz Pe H H sTn1 H 285 Ir 3 Pz Pe H H sTn3 H 286 Ir 3 Pz Pe H H sPr H287 Ir 3 Pz Pe H H sPe H 288 Ir 3 Pz Cn1 H H sPh H 289 Ir 3 Pz Cn1 H HsNp1 H 290 Ir 3 Pz Cn1 H H sNp2 H 291 Ir 3 Pz Cn1 H H sTn1 H 292 Ir 3 PzCn1 H H sTn3 H 293 Ir 3 Pz Cn1 H H sPr H 294 Ir 3 Pz Cn1 H H sPe H 295Ir 3 Pz Cn2 H H sPh H 296 Ir 3 Pz Cn2 H H sNp1 H 297 Ir 3 Pz Cn2 H HsNp2 H 298 Ir 3 Pz Cn2 H H sTn1 H 299 Ir 3 Pz Cn2 H H sTn3 H 300 Ir 3 PzCn2 H H sPr H 301 Ir 3 Pz Cn2 H H sPe H 302 Ir 3 Pz Cz H H sPh H 303 Ir3 Pz Cz H H sNp1 H 304 Ir 3 Pz Cz H H sNp2 H 305 Ir 3 Pz Cz H H sTn1 H306 Ir 3 Pz Cz H H sTn3 H 307 Ir 3 Pz Cz H H sPr H 308 Ir 3 Pz Cz H HsPe H 309 Ir 3 Py1 Ph H H sPh H 310 Ir 3 Py1 Ph H H sNp1 H 311 Ir 3 Py1Ph H H sTn1 H 312 Ir 3 Py1 Ph H H sTn3 H

TABLE 7 No M m CyN1 CyC1 R1 R2 R3 R4 313 Ir 3 Py1 Tn1 H H sPh H 314 Ir 3Py1 Tn1 H H sNp1 H 315 Ir 3 Py1 Tn1 H H sTn1 H 316 Ir 3 Py1 Tn1 H H sTn3H 317 Ir 3 Py1 Tn3 H H sPh H 318 Ir 3 Py1 Tn3 H H sNp1 H 319 Ir 3 Py1Tn3 H H sTn1 H 320 Ir 3 Py1 Tn3 H H sTn3 H 321 Ir 3 Py1 Tn4 H H sPh H322 Ir 3 Py1 Tn4 H H sNp1 H 323 Ir 3 Py1 Tn4 H H sTn1 H 324 Ir 3 Py1 Tn4H H sTn3 H 325 Ir 3 Py1 Np2 H H sPh H 326 Ir 3 Py1 Np2 H H sNp1 H 327 Ir3 Py1 Np2 H H sTn1 H 328 Ir 3 Py1 Np2 H H sTn3 H 329 Ir 3 Py2 Ph H H sPhH 330 Ir 3 Py2 Ph H H sNp1 H 331 Ir 3 Py2 Ph H H sTn1 H 332 Ir 3 Py2 PhH H sTn3 H 333 Ir 3 Py2 Tn1 H H sPh H 334 Ir 3 Py2 Tn1 H H sNp1 H 335 Ir3 Py2 Tn1 H H sTn1 H 336 Ir 3 Py2 Tn1 H H sTn3 H 337 Ir 3 Py2 Tn3 H HsPh H 338 Ir 3 Py2 Tn3 H H sNp1 H 339 Ir 3 Py2 Tn3 H H sTn1 H 340 Ir 3Py2 Tn3 H H sTn3 H 341 Ir 3 Py2 Tn4 H H sPh H 342 Ir 3 Py2 Tn4 H H sNp1H 343 Ir 3 Py2 Tn4 H H sTn1 H 344 Ir 3 Py2 Tn4 H H sTn3 H 345 Ir 3 Py2Np2 H H sPh H 346 Ir 3 Py2 Np2 H H sNp1 H 347 Ir 3 Py2 Np2 H H sTn1 H348 Ir 3 Py2 Np2 H H sTn3 H 349 Ir 3 Pr Ph sPh H H H 350 Ir 3 Pr Ph sNp2H H H 351 Ir 3 Pr Ph sTn1 H H H 352 Ir 3 Pr Ph sTn3 H H H 353 Ir 3 PrTn1 sPh H H H 354 Ir 3 Pr Tn1 sNp2 H H H 355 Ir 3 Pr Tn1 sTn1 H H H 356Ir 3 Pr Tn1 sTn3 H H H 357 Ir 3 Pr Tn3 sPh H H H 358 Ir 3 Pr Tn3 sNp2 HH H 359 Ir 3 Pr Tn3 sTn1 H H H 360 Ir 3 Pr Tn3 sTn3 H H H 361 Ir 3 PrNp2 sPh H H H 362 Ir 3 Pr Np2 sNp2 H H H 363 Ir 3 Pr Np2 sTn1 H H H 364Ir 3 Pr Np2 sTn3 H H H

TABLE 8 No M m CyN1 CyC1 R1 R2 R3 R4 365 Ir 3 Pz Ph sPh H H H 366 Ir 3Pz Ph sNp2 H H H 367 Ir 3 Pz Ph sTn1 H H H 368 Ir 3 Pz Ph sTn3 H H H 369Ir 3 Pz Tn1 sPh H H H 370 Ir 3 Pz Tn1 sNp2 H H H 371 Ir 3 Pz Tn1 sTn1 HH H 372 Ir 3 Pz Tn1 sTn3 H H H 373 Ir 3 Pz Tn3 sPh H H H 374 Ir 3 Pz Tn3sNp2 H H H 375 Ir 3 Pz Tn3 sTn1 H H H 376 Ir 3 Pz Tn3 sTn3 H H H 377 Ir3 Pz Np2 sPh H H H 378 Ir 3 Pz Np2 sNp2 H H H 379 Ir 3 Pz Np2 sTn1 H H H380 Ir 3 Pz Np2 sTn3 H H H

TABLE 9 No M m CyN1 CyC1 R1 R2 R3 R4 R5 R6 381 Ir 3 Pr Ph sPh H H H H—NO2 382 Ir 3 Pr Ph sNp2 H —CH3 H H H 383 Ir 3 Pr Ph sTn1 H H H —CF3 H384 Ir 3 Pr Ph sTn3 H H H H sPh 385 Ir 3 Pr Tn1 sPh H H H —OCH₃ H 386 Ir3 Pr Tn1 sNp2 H H H H sPh 387 Ir 3 Pr Tn1 sTn1 H H H H —CF3 388 Ir 3 PrTn1 sTn3 H H H H sPh 389 Ir 3 Pr Tn3 sPh H H H —OCH₃ H 390 Ir 3 Pr Tn3sNp2 H H H H —OCH₃ 391 Ir 3 Pr Tn3 sTn1 H H H H —OCH₃ 392 Ir 3 Pr Tn3sTn3 H H H —OCH₃ H 393 Ir 3 Pr Np2 sPh H H H —OCH₃ H 394 Ir 3 Pr Np2sNp2 H H H H sPh 395 Ir 3 Pr Np2 sTn1 H H H H sPh 396 Ir 3 Pr Np2 sTn3 HH H H —OCH₃ 397 Ir 3 Pz Ph sPh H H —OCH₃ H H 398 Ir 3 Pz Ph sNp2 H H—OCH₃ H H 399 Ir 3 Pz Ph sTn1 H H H H —OCH₃ 400 Ir 3 Pz Ph sTn3 H H H H—OCH₃ 401 Ir 3 Pz Tn1 sPh H —C3H7 H H H 402 Ir 3 Pz Tn1 sNp2 H H H H H403 Ir 3 Pz Tn1 sTn1 H H H H H 404 Ir 3 Pz Tn1 sTn3 H H H H sPh 405 Ir 3Pz Tn3 sPh H H H H —OCH₃ 406 Ir 3 Pz Tn3 sNp2 H H —OCH₃ H H 407 Ir 3 PzTn3 sTn1 H H —OCH₃ H H 408 Ir 3 Pz Tn3 sTn3 H H H H —OCH₃ 409 Ir 3 PzNp2 sPh H H H H —OCH₃ 410 Ir 3 Pz Np2 sNp2 H —C3H7 H H H

TABLE 10 No M m CyN1 CyC1 R1 R2 R3 R4 R5 R6 411 Ir 3 Pz Np2 sTn1 H H—CF3 H H 412 Ir 3 Pz Np2 sTn3 H H —CF3 H H 413 Ir 3 Ta Ph C4H9 C4H9 sPhH OCH3 H 414 Ir 3 Pr Ph sPh H H H H H 415 Ir 3 Pr Ph sNp2 H —CH3 H H H416 Ir 3 Pr Ph sTn1 H H H H H 417 Ir 3 Pr Ph sTn3 H H H H H 418 Ir 3 PrTn1 sPh H H H —OCH₃ H 419 Ir 3 Pr Tn1 sNp2 H H H H H 420 Ir 3 Pr Tn1sTn1 H H H H H 421 Ir 3 Pr Tn1 sTn3 H H H H H 422 Ir 3 Pr Tn3 sPh H H H—OCH₃ H 423 Ir 3 Pr Tn3 sNp2 H H H H H 424 Ir 3 Pr Tn3 sTn1 H —NO2 H H H425 Ir 3 Pr Tn3 sTn3 H H H H H 426 Ir 3 Pr Np2 sPh H H H H H 427 Ir 3 PrNp2 sNp2 H H H H H 428 Ir 3 Pr Np2 sTn1 H H H H H 429 Ir 3 Pr Np2 sTn3 HH H H H 430 Ir 3 Pz Ph sPh H H —F H H 431 Ir 3 Pz Ph sNp2 H H H H H 432Ir 3 Pz Ph sTn1 —CN H H H H 433 Ir 3 Pz Ph sTn3 H H H H H 434 Ir 3 PzTn1 sPh H —C3H7 H H H 435 Ir 3 Pz Tn1 sNp2 H H —CH2— H H CH═CH —CH3 436Ir 3 Pz Tn1 sTn1 H H H H H 437 Ir 3 Pz Tn1 sTn3 H H H H H 438 Ir 3 PzTn3 sPh H —SC3H7 H H H 439 Ir 3 Pz Tn3 sNp2 H H H H H 440 Ir 3 Pz Tn3sTn1 H H H H H 441 Ir 3 Pz Tn3 sTn3 H H H H 442 Ir 3 Pz Np2 sPh H H H HH 443 Ir 3 Pz Np2 sNp2 H H H H H 444 Ir 3 Pz Np2 sTn1 H H H H H 445 Ir 3Pz Np2 sTn3 H H H H H

TABLE 11 No M m n CyN1 CyC1 CyN2 CyC2 R1 R2 R3 R4 R1′ R2′ R3′ R4′ 446 Ir2 1 Pr Ph Pr Tn1 sPh H H H sPh H H H 447 Ir 2 1 Pr Ph Pr Tn1 sNp2 H H HsNp2 H H H 448 Ir 2 1 Pr Ph Pr Tn1 sTn1 H H H sTn1 H H H 449 Ir 2 1 PrPh Pr Tn1 sTn3 H H H sTn3 H H H 450 Ir 2 1 Pr Tn3 Pr Np2 sPh H H H sPh HH H 451 Ir 2 1 Pr Tn3 Pr Np2 sNp2 H H H sNp2 H H H 452 Ir 2 1 Pr Tn3 PrNp2 sTn1 H H H sTn1 H H H 453 Ir 2 1 Pr Tn3 Pr Np2 sTn3 H H H sTn3 H H H

TABLE 12 No M m n CyN1 CyC1 E G R1 R2 R3 R4 454 Ir Ir 1 Pr Ph —CH3 —CH3sPh H H H 455 Ir Ir 1 Pr Ph —CH3 —CH3 sNp2 H H H 456 Ir Ir 1 Pr Ph —CH3—CH3 sTn1 H H H 457 Ir Ir 1 Pr Ph —CH3 —CH3 H H sTn3 H 458 Ir Ir 1 PrTn3 —CH3 sPh H H sPh H 459 Ir Ir 1 Pr Tn3 —CH3 sPh H H sNp2 H 460 Ir Ir1 Pr Tn3 —CH3 sPh H H sTn1 H 461 Ir Ir 1 Pr Tn3 —CH3 sPh H H sTn3 H

TABLE 13 No M m CyN1 CyC1 R1 R2 R3 R4 462 Rh 3 Pr Ph sPh H H H 463 Rh 3Pr Ph sNp2 H H H 464 Rh 3 Pr Ph sTn1 H H H 465 Rh 3 Pr Ph sTn3 H H H 466Rh 3 Pr Tn1 sPh H H H 467 Rh 3 Pr Tn1 sNp2 H H H 468 Rh 3 Pr Tn1 sTn1 HH H 469 Rh 3 Pr Tn1 sTn3 H H H 470 Rh 3 Pr Tn3 sPh H H H 471 Rh 3 Pr Tn3sNp2 H H H 472 Rh 3 Pr Tn3 sTn1 H H H 473 Rh 3 Pr Tn3 sTn3 H H H 474 Rh3 Pr Np2 sPh H H H 475 Rh 3 Pr Np2 sNp2 H H H 476 Rh 3 Pr Np2 sTn1 H H H477 Rh 3 Pr Np2 sTn3 H H H

TABLE 14 No M m CyN1 CyC1 R1 R2 R3 R4 478 Pt 2 Pr Ph sPh H H H 479 Pt 2Pr Ph sNp2 H H H 480 Pt 2 Pr Ph sTn1 H H H 481 Pt 2 Pr Ph sTn3 H H H 482Pt 2 Pr Tn1 sPh H H H 483 Pt 2 Pr Tn1 sNp2 H H H 484 Pt 2 Pr Tn1 sTn1 HH H 485 Pt 2 Pr Tn1 sTn3 H H H 486 Pt 2 Pr Tn3 sPh H H H 487 Pt 2 Pr Tn3sNp2 H H H 488 Pt 2 Pr Tn3 sTn1 H H H 489 Pt 2 Pr Tn3 sTn3 H H H 490 Pt2 Pr Np2 sPh H H H 491 Pt 2 Pr Np2 sNp2 H H H 492 Pt 2 Pr Np2 sTn1 H H H493 Pt 2 Pr Np2 sTn3 H H H

TABLE 15 No M m CyN1 CyC1 R1 R2 R3 R4 494 Pd 2 Pr Ph sPh H H H 495 Pd 2Pr Ph sNp2 H H H 496 Pd 2 Pr Ph sTn1 H H H 497 Pd 2 Pr Ph sTn3 H H H 498Pd 2 Pr Tn1 sPh H H H 499 Pd 2 Pr Tn1 sNp2 H H H 500 Pd 2 Pr Tn1 sTn1 HH H 501 Pd 2 Pr Tn1 sTn3 H H H 502 Pd 2 Pr Tn3 sPh H H H 503 Pd 2 Pr Tn3sNp2 H H H 504 Pd 2 Pr Tn3 sTn1 H H H 505 Pd 2 Pr Tn3 sTn3 H H H 506 Pd2 Pr Np2 sPh H H H 507 Pd 2 Pr Np2 sNp2 H H H 508 Pd 2 Pr Np2 sTn1 H H H509 Pd 2 Pr Np2 sTn3 H H H

TABLE 16 No M m CyN1 CyC1 R1 R2 R3 R4 R5 R6 510 Ir 3 Pr Ph sPe H H H H H511 Ir 3 Pr Ph sPh H sPh H

H 512 Ir 3 Pr Ph H

sPh H H

513 Ir 3 Pr Np2 sPe H H H H H 514 Ir 3 Pr Np2 H H sTn1 H CH3 H 515 Ir 3Pr Tn1 CH3 H sTn1 H CH3 H 516 Ir 3 Pr Tn1 sPh H sTn1 H sPh H

TABLE 17 No M m n CyN1 CyC1 R1 R2 R3 R4 E G 517 Ir 2 1 Pr Tn3 H H sPh HCH3 CH3 518 Ir 2 1 Pr Tn1 H H sTn1 H CH3 CH3 519 Ir 2 1 Pr Np2 H H sNp2H CH3 CH3 520 Ir 3 0 Py1 Ph sPh H H H — — 521 Ir 3 0 Py1 Ph sNp1 H H H —— 522 Ir 3 0 Pr Ph H H H sPh — — 523 Ir 3 0 Pr Ph H sPh H H — — 524 Ir 30 Pr Tn1 Ph H H H — — 525 Ir 2 1 Py1 Ph sPh H H H CH3 CH3 526 Ir 2 1 Py1Ph sNp1 H H H CH3 CH3 527 Ir 2 1 Pr Ph H H H sPh CH3 CH3 528 Ir 2 1 PrPh H sPh H H CH3 CH3 529 Ir 2 1 Pr Tn1 Ph H H H CH3 CH3

Hereinbelow, the present invention will be described more specificallybased on Examples.

EXAMPLES 1-6

Each of luminescence devices having a layer structure shown in FIG. 1Bwere prepared in the following manner.

On a 1.1 mm-thick glass substrate (transparent substrate 15), a 100nm-thick film (transparent electrode 14) of ITO (indium tin oxide) wasformed by sputtering, followed by patterning to form a stripe electrodeincluding 100 lines each having a width of 100 nm and a spacing with anadjacent line of 10 nm (i.e., electrode pitch of 110 nm).

On the ITO-formed substrate, three organic layers and two metalelectrode layers shown below were successively formed by vacuum (vapor)deposition using resistance heating in a vacuum chamber (10⁻⁴ Pa).

Organic layer 1 (hole transport layer 13) (40 nm): α-NPD

Organic layer 2 (luminescence layer 12) (30 nm): co-deposited film ofCBP:metal complex (metal coordination compound shown in Table 20) (95:5by weight)

Organic layer 3 (electron transport layer 16) (30 nm): Alq3

Metal electrode layer 1 (metal electrode 11) (15 nm): Al—Li alloy(Li=1.8 wt. %)

Metal electrode layer 2 (metal electrode 11) (100 nm): Al

The above-deposited metal electrode layers 1 and 2 (Al—Li layer and Allayer) had a stripe electrode pattern including 100 lines each having awidth of 100 nm and a spacing of 10 nm (electrode pitch=110 nm) andarranged so that the stripe electrode pattern intersected with that ofthe ITO electrode at right angles to form a matrix of pixels each havingan effective electrode area of 3 mm² comprising 20 ITO lines bundledtogether at a lead-out portion and 15 Al (Al—Li) lines bundled togetherat a lead-out portion.

Each of the thus-prepared luminescence devices was taken out of thevacuum chamber and was subjected to a continuous energization (currentpassage) test in an atmosphere of dry nitrogen gas stream so as toremove device deterioration factors, such as oxygen and moisture (watercontent).

The continuous energization test was performed by continuously applyinga voltage at a constant current density of 50 mA/cm² to the luminescencedevice having the ITO (transparent) electrode (as an anode) and the Al(metal) electrode (as a cathode), followed by measurement of emissionluminance (brightness) with time so as to determine a time (luminancehalf-life) required for decreasing an initial luminance (60-220 cd/m²)to ½ thereof.

The results are shown in Table 18 appearing hereinafter.

COMPARATIVE EXAMPLE 1

A comparative luminescence device was prepared and evaluated in the samemanner as in Examples 1-6 except that the Ir complexes (metalcoordination compounds shown in Table 20) was changed toIr-phenylpyridine complex (Ir(ppy)₃) shown below.

The results are also shown in Table 18 below.

TABLE 18 Ex. No. Compound No. Luminance half-life (Hr) Ex. 1 3 450 Ex. 211 550 Ex. 3 22 500 Ex. 4 43 500 Ex. 5 45 600 Ex. 6 385 400 Ex. 7 413650 Comp.Ex. 1 Ir(ppy)₃ 300

As is apparent from Table 18, compared with the conventionalluminescence device using Ir(ppy)₃, the luminescence devices using themetal coordination compounds of formula (1) according to the presentinvention provide longer luminance half-lives, thus resulting in an ELdevice having a high durability (luminance stability) based on a goodstability of the metal coordination compound of formula (1) of thepresent invention.

EXAMPLE 7

A color organic EL display apparatus shown in FIG. 2 was prepared in thefollowing manner.

An active matrix substrate had a planar structure basically similar to astructure described in U.S. Pat. No. 6,114,715.

Specifically, on a 1.1 mm-thick glass substrate, top state-type TFTs ofpolycrystalline silicon were formed in an ordinary manner and thereon, aflattening film was formed with contact holes for electrical connectionwith a pixel electrode (anode) at respective source regions, thuspreparing an active matrix substrate with a TFT circuit.

On the active matrix substrate, a 700 nm-thick pixel electrode (anode)of ITO having a larger work function was formed in a prescribed pattern.On the ITO electrode, prescribed organic layers and a 100 nm-thick Alelectrode (cathode) were successively formed by vacuum deposition with ahard mask, followed by patterning to form a matrix of color pixels(128×128 pixels).

The respective organic layers corresponding to three color pixels (red(R) green (G) and blue (B)) were consisting of the following layers.

<R Pixel Region>

α-NPD (40 nm)/CBP: Ex. Comp. No. 22 (93:7 by weight) (30 nm)/BCP (20nm)/Alq 3 (40 nm)

<G Pixel Region>

α-NPD (50 nm)/Alq 3 (50 nm)

<B Pixel Region>

α-NPD (50 nm)/BCP (20 nm)/Alq 3 (50 nm)

When the thus-prepared color organic EL display apparatus was driven,desired color image data can be displayed stably with good imagequalities.

EXAMPLE 8 Synthesis of Example Compound No. 22

In a 500 ml-three-necked flask, 12.6 g (85.2 mM) of2,5-dichloropyridine, 15.2 g (85.4 mM) of benzothiophene-2-boronic acid,75 ml of toluene, 37.5 ml of ethanol and 75 ml of 2M-sodium carbonateaqueous solution were placed and stirred at room temperature undernitrogen stream, and 3.06 g (2.64 mM) oftetrakis(triphenylphosphine)palladium (0) was added thereto, followed byrefluxing under stirring for 8 hours under nitrogen stream. After thereaction, the reaction mixture was cooled on an ice bath to precipitatea crystal, which was then filtered out and washed with water. To thecrystal, 100 ml of methanol was added and washed under stirring at roomtemperature, followed by filtration to recover the crystal. The crystalwas purified by silica gel column chromatography (eluent: chloroform)and recrystallized from a mixture solvent of chloroform-methanol toobtain 11.8 g (Yield: 56.4%) of 5-chloro-2-(benzo[b]thienyl)pyridine(colorless crystal).

In a 100 ml-three-necked flask, 4.91 g (20.0 mM) of5-chloro-2-(benzo[b]thienyl)pyridine, 3.66 g (30.0 mM) of phenylboronicacid, 9.58 g (40.0 mM) of tripotassium phosphate hydrate, 3.2 mg (0.020mM) of palladium (II) acetate, 11.9 mg (0.040 mM) of2-ditert-butylphosphinobiphenyl and 60 ml of toluene were placed andrefluxed under stirring for 24 hours at 100° C. under nitrogen stream.After the reaction, the reaction mixture was cooled on an ice bath toprecipitate a crystal, which was then filtered out and washed withwater. To the crystal, 25 ml of methanol was added and washed understirring at room temperature, followed by recovery by filtration. Thecrystal was purified by silica gel column chromatography (eluent:chloroform) and recrystallized from a chloroform-methanol mixturesolvent to obtain 1.17 g (Yield: 20.4%) of2-(benzo[b]thienyl)-5-phenylpyridine (colorless crystal).

In a 100 ml-four-necked flask, 50 ml of glycerol was placed and heatedat 130-140° C. under stirring and bubbling with nitrogen for 2 hours.Then, the glycerol was cooled by standing to 100° C., and 1.15 g (4.00mM) of 2-(benzo[b]thienyl)-5-phenylpyridine and 0.40 g (0.82 mM) ofiridium (III) acetylacetonate were added thereto, followed by stirringfor 5 hours at 180-235° C. under nitrogen stream. The reaction mixturewas cooled to room temperature and poured into 300 ml of IN-hydrochloricacid to form a precipitate. The precipitate was recovered by filtrationand washed with water, followed by drying for 5 hours at 100° C. underreduced pressure. The resultant precipitate was silica gel columnchromatography (eluent: chloroform) to obtain 0.26 g (Yield: 30.2%) ofred powdery tris[2-(benzo-[b]thienyl)-5-phenylpyridine-C²,N]iridium(III).

According to MALDI-TOF MS (matrix-assisted laser desorptionionization-time of flight mass spectroscopy), the compound exhibited M⁺(mass number of the corresponding cation formed by removal of 1electron) of 1051.2, thus confirming the objective iridium complex.

When the compound was dissolved in toluene and subjected to measurementof phosphorescence spectrum at an excited light wavelength of 380 nm byusing a fluorescence spectrometer, the compound exhibited aphosphorescence spectrum showing λmax (maximum emission wavelength) of620 nm, thus confirming clear red luminescence.

When the luminescence device prepared in Example 3 using theabove-synthesized metal coordination compound (Ex. Comp. No. 22) wassubjected to measurement of phosphorescence spectrum in a similarmanner, a clear red luminescence was confirmed similarly as in the caseof the compound in toluene described above.

EXAMPLE 9 Synthesis of Ex. Comp. No. 11

A metal coordination compound (Ex. Comp. No. 11) was synthesized throughthe following reaction schemes. Hereinafter, the synthesis yield issimply represented by “Y”.

According to MALDI-TOF MS, the compound exhibited M⁺=919.0, thus beingidentified as the objective iridium compound.

When the compound was dissolved in toluene and subjected to measurementof phosphorescence spectrum at an excited light wavelength of 400 nm byusing a fluorescence spectrometer, the compound exhibited aphosphorescence spectrum showing λmax (maximum emission wavelength) of612 nm, thus confirming clear red luminescence.

When a luminescence device having a layer structure shown below andusing the above-synthesized metal coordination compound (Ex. Comp. No.11) was prepared and subjected to measurement of phosphorescencespectrum in a similar manner, a clear red luminescence was confirmedsimilarly as in the case of the compound in toluene described above.

ITO (100 nm)/α-NPD (40 nm)/CBP: Ex. Comp. No. 11 (95:5 by weight)(30nm)/BCP (20 nm)/Alq3 (40 nm)/Al—Li (1 nm)/Al (100 nm).

Further, the luminescence device exhibited a good rectifyingcharacteristic.

Specifically, FIG. 3A is a graph showing a relationship between anelectric field strength (E) and a current density of the luminescencedevice, and FIG. 3B is a graph showing a relationship between anelectric field strength (E) and a luminance (L) of the luminescencedevice. Further, FIG. 3C shows a luminescence spectrum of theluminescence device under application of a voltage of 10 volts.

The luminescence device exhibited a luminescence efficiency of 0.8 lm/Wunder application of a voltage of 10 volts. The luminescence device alsoemitted stable luminescence even when the luminescence device wascontinuously supplied with the voltage for ca. 200 hours.

EXAMPLE 10 Synthesis of Ex. Comp. No. 45

A metal coordination compound (Ex. Comp. No. 45) was synthesized throughthe following reaction schemes.

According to MALDI-TOF MS, the compound exhibited M⁺=1183.3, thus beingidentified as the objective iridium compound.

When the compound was dissolved in toluene and subjected to measurementof phosphorescence spectrum at an excited light wavelength of 380 nm byusing a fluorescence spectrometer, the compound exhibited aphosphorescence spectrum showing λmax (maximum emission wavelength) of603 nm, thus confirming clear reddish orange luminescence.

When the luminescence device prepared in Example 5 using theabove-synthesized metal coordination compound (Ex. Comp. No. 45) wassubjected to measurement of phosphorescence spectrum in a similarmanner, a clear reddish orange luminescence was confirmed similarly asin the case of the compound in toluene described above.

Further, the luminescence device exhibited a good rectifyingcharacteristic.

The luminescence device exhibited a luminescence efficiency of 0.5 lm/Wunder application of a voltage of 8 volts. The luminescence device alsoemitted stable luminescence even when the luminescence device wascontinuously supplied with the voltage for ca. 150 hours.

EXAMPLE 11 Another Synthesis of Ex. Comp. No. 22

Tris[2-(benzo[b]thienyl)-5-phenylpyridine-C²,N]iridium (III) (Ex. Comp.No. 22) prepared in Example 8 was synthesized through another reactionschemes shown below.

In a 200 ml-three-necked flask, 0.58 mg (1.64 mmole) of iridium (III)chloride-trihydrate (made by Across Organics Co.), 1.5 g (5.22 mmole) of2-(benzo[b]thienyl)-5-phenylpyridine, 45 ml of ethoxyethanol and 15 mlof water were placed and stirred for 30 min. at room temperature undernitrogen stream, followed by 24 hours of reflux under stirring. Thereaction product was cooled to room temperature, and the precipitate wasrecovered by filtration and washed with water, followed successivewashing with ethanol and acetone. After drying under a reduced pressureat room temperature, 1.02 g of red powderytetrakis[2-(benzo[b]thienyl)-5-phenylpyridine-C²,N]-(μ-dichloro)diiridium(III) was obtained.

In a 200 ml-three-necked flask, 70 ml of ethoxyethanol, 0.95 g (0.72mmole) of tetrakis[2-(benzo[b]thienyl)-5-phenylpyridine-C²N](μ-dichloro)-diiridium (III), 0.22 g (2.10 mM) of acetylacetone and1.04 g (9.91 mM) of sodium carbonate, were placed and stirred for 1 hourat room temperature under nitrogen stream and then refluxed understirring for 15 hours. The reaction product was cooled with ice, and theprecipitate was filtered out and washed with water. The precipitate wasthen purified by silica gel column chromatography (eluent:chloroform/methanol=30/1) to obtain 0.43 g of red powderybis[2-(benzo[b]thienyl)-5-phenylpyridine-C²,N](acetylacetonato)-iridium(III) (Example Compound No. 517). According to MALDI-TOF MS, M⁺ of 864.2of the compound was confirmed. A toluene solution of the compoundexhibited a luminescence spectrum showing λmax=631 nm and a quantumyield of 0.18 relative to 1.0 of Ir(ppy)₃.

In a 100 ml-three-necked flask, 0.27 g (0.94 mM) of2-(benzo[b]thienyl)-5-phenylpyridine, 0.36 g (0.42 mM) ofbis[2-benzo[b]thienyl)-5-phenylpyridine-C²,N](acetylacetonato)iridium(III) and 25 ml of glycerol, were placed and heated around 180° C. for 8hours under stirring and nitrogen stream. The reaction product wascooled to room temperature and poured into 170 ml of 1N-hydrochloricacid, and the precipitate was filtered out, washed with water and driedat 100° C. under a reduced pressure for 5 hours. The precipitate waspurified by silica gel column chromatography with chloroform as theeluent to obtain 0.27 g of red powderytris[2-(benzo[g]thienyl-5-phenylpyridine-C²,N]iridium (III) (ExampleCompound No. 22). According to MALDI-TOF MS, M⁺ of 1051.2 of thecompound was confirmed. A toluene solution of the compound exhibited aluminescence spectrum showing λmax=627 nm and a quantum yield of 0.17relative to 1.0 of Ir(ppy)₃.

The above-synthesized compound and a luminescence device prepared byusing the compound exhibited luminescence characteristics similar tothose of the compound and luminescence device prepared in Example 8.

Bis[2-(benzo[g]thienyl)-5-phenylpyridine-C²,N]iridium (III) (Ex. Comp.No. 517) prepared in this example as an intermediate product exhibitedλmax which was longer by ca. 4 nm than that of the final product (Ex.Comp. No. 22) having three identical ligands. Further, when aluminescence device using the intermediate product was prepared andevaluated in the same manner as in Example 8, the luminescence deviceexhibited a luminescence spectrum showing λmax=631 nm. Accordingly, theintermediate product used in this example can also be used as aluminescence material.

EXAMPLE 12 Another Synthesis of Ex. Comp. No. 45

The metal coordination compound (Ex. Comp. No. 45) prepared in Example10 was synthesized through another reaction schemes shown below.

In a 200 ml-three-necked flask, 0.58 mg (1.64 mmole) of iridium (III)chloride-trihydrate (made by Across Organics Co.), 1.7 g (5.1 mmole) ofa compound (1), 45 ml of ethoxyethanol and 15 ml of water were placedand stirred for 30 min. at room temperature under nitrogen stream,followed by 24 hours of reflux under stirring. The reaction product wascooled to room temperature, and the precipitate was recovered byfiltration and washed with water, followed successive washing withethanol and acetone. After drying under a reduced pressure at roomtemperature, 1.0 g (yield=93.4%) of red powdery compound (2) wasobtained.

In a 200 ml-three-necked flask, 70 ml of ethoxyethanol, 0.90 g (0.71mmole) of the compound (2), 0.22 g (2.10 mmole) of acetylacetone and1.04 g (9.91 mmole) of sodium carbonate, were placed and stirred for 1hour at room temperature under nitrogen stream and then refluxed understirring for 15 hours. The reaction product was cooled with ice, and theprecipitate was filtered out and washed with water. The precipitate wasthen purified by silica gel column chromatography (eluent:chloroform/methanol=30/1) to obtain 0.39 g of red powdery compound (3)(Example Compound No. 519). According to MALDI-TOF MS, M⁺ of 952.3 ofthe compound was confirmed. A toluene solution of the compound exhibiteda luminescence spectrum showing λmax=608 nm and a higher quantum yieldof 0.30 relative to 1.0 of Ir(ppy)₃ in this emission wavelength region.

In a 100 ml-three-necked flask, 0.29 g (0.88 mM) of the compound (1)0.34 g (0.35 mM) of the compound (3) and 25 ml of glycerol, were placedand heated around 180° C. for 8 hours under stirring and nitrogenstream. The reaction product was cooled to room temperature and pouredinto 170 ml of 1N-hydrochloric acid, and the precipitate was filteredout, washed with water and dried at 100° C. under a reduced pressure for5 hours. The precipitate was purified by silica gel columnchromatography with chloroform as the eluent to obtain 0.23 g of redpowdery compound (4) (Example Compound No. 45). According to MALDI-TOFMS, M⁺ of 1183.4 of the compound was confirmed. A toluene solution ofthe compound exhibited a luminescence spectrum showing λmax=603 nm and aquantum yield of 0.278 relative to 1.0 of Ir(ppy)₃.

The above-synthesized compound and a luminescence device prepared byusing the compound exhibited luminescence characteristics similar tothose of the compound and luminescence device prepared in Example 10.

The compound (3) (Ex. Comp. No. 519) prepared in this example as anintermediate product exhibited λmax which was longer by ca. 4 nm thanthat of the final product (Ex. Comp. No. 45) having three identicalligands. Further, when a luminescence device using the intermediateproduct was prepared and evaluated in the same manner as in Example 10,the luminescence device exhibited a luminescence spectrum showingλmax=608 nm and an external luminescence yield of 0.7 lm/W. Further, theluminescence device emitted stable luminescence even when continuouslysupplied with the voltage for ca. 100 hours. Accordingly, theintermediate product used in this example can also be used as aluminescence material.

EXAMPLE 13 Synthesis of Ex. Comp. Nos. 520 and 525

It is easy to synthesize the following compounds in the same manner asin Example 11 except that 4-chloropyrimidine is synthesized from4(3H)-pyrimidone (made by Aldrich Co.) in the same manner as the processdescribed at pages 37 and 38 of JP-A (Tokuhyo) 2001-504113 (corr. toU.S. Pat. No. 6,300,330) and is reacted with 4-phenylboronic acid (madeby Lancaster Co.) to obtain 4-(biphenyl-4-yl)pyrimidine, which is usedinstead of 2-(benzo[b]thienyl)-5-phenylpyridine.

Bis[4-(biphenyl-4-yl)pyridine-C³,N³] (acetylacetonato) iridium (III)(Ex. Comp. No. 520).

Tris[4-(biphenyl-4-yl)pyrimidine-C³,N³] iridium (III) (Ex. Comp. No.525).

EXAMPLE 14 Synthesis of Ex. Comp. Nos. 521 and 526

It is easy to synthesize the following compounds in the same manner asin Example 11 except that 4-(4-chlorophenyl)pyrimidine is synthesizedfrom 4-chloropyrimidine prepared in Example 13 and 4-chlorophenylboronicacid (made by Aldrich Co.) and was reacted with 2-naphthaleneboronicacid (made by Lancaster Co.) to obtain4-[4-(2-naphthyl)phenyl]-pyrimidine, which is used instead of2-(benzo[b]thienyl)-5-phenylpyridine.

Bis{4-[4-(2-naphthyl)phenyl]pyrimidine-C³, N³}(acetylacetonato)iridium(III) (Ex. Comp. No. 521).

Tris{4-[4-(2-naphthyl)phenyl]pyrimidine-C³,N³}iridium (III) (Ex. Comp.No. 526).

EXAMPLE 15 Synthesis of Ex. Comp. Nos. 522 and 527

It is easy to synthesize the following compounds in the same manner asin Example 11 except that 2,4-diphenylpyridine is synthesized fromphenylboronic acid (made by Tokyo Kasei Kogyo K.K.) and4-phenyl-2-bromopyridine (made by General Intermediates of Canada) andwas used instead of 2-(benzo[b]thienyl)-5-phenylpyridine.

Bis(2,4-diphenylpyridine-C²,N¹)(acetylacetonato)iridium (III) (Ex. Comp.No. 522).

Tris(2,4-diphenylpyridine-C²,N¹)iridium (III) (Ex. Comp. No. 527).

EXAMPLE 16 Synthesis of Ex. Comp. Nos. 523 and 528

It is easy to synthesize the following compounds in the same manner asin Example 11 except that 2-(biphenyl-3-yl)pyridine is synthesized from3-biphenylboronic acid (made by Lancaster Co.) and 2-bromopyridine (madeby Tokyo Kasei Kogyo K.K.) and is used instead of2-(benzo[b]thienyl)-5-phenylpyridine.

Bis[2-(biphenyl-3-yl)pyridine-C⁴,N³)(acetylacetonato)iridium (III) (Ex.Comp. No. 523).

Tris[2-(biphenyl-2-yl)pyridine-C⁴,N³)iridium (III) (Ex. Comp. No. 528).

EXAMPLE 17 Synthesis of Ex. Comp. Nos. 524 and 529

It is easy to synthesize the following compounds in the same manner asin Example 11 except that 2-(5-bromothiophene-2-yl)pyridine issynthesized from 2-bromopyridine (made by Tokyo Kasei Kogyo K.K.) and5-bromothiophene-2-boronic acid (made by Aldrich Co.) and was reactedwith phenylboronic acid (made by Tokyo Kasei Kogyo K.K.) to obtain2-(5-phenylthiophene-2-yl)pyridine, which is used instead of2-(benzo[b]thienyl)-5-phenylpyridine.

Bis[2-(5-phenylthiophene-2-yl)pyridine-C²,N¹)(acetylacetonato)iridium(III) (Ex. Comp. No. 524).

Tris[2-(5-phenylthiophene-2-yl)pyridine-C²,N¹)iridium (III) (Ex. Comp.No. 529).

As described above, according to the present invention, the metalcoordination compound of the formula (1) characterized by aromaticsubstituent. The electroluminescence device (luminescence device) of thepresent invention using, as a luminescent center material, the metalcoordination compound of the formula (1) is an excellent device whichnot only allows high-efficiency luminescence but also retains a highluminance for a long period and shows little deterioration by currentpassage. Further, the display apparatus using the electroluminescencedevice of the present invention exhibits excellent display performances.

1. A metal coordination compound represented by one of followingformulas (a) or (b):


2. An electroluminescence device, comprising: a pair of electrodesdisposed on a substrate, and a luminescence unit comprising at least oneorganic compound disposed between the electrodes, wherein the organiccompound comprises a metal coordination compound represented by theformula (a) or (b) in claim
 1. 3. The electroluminescence deviceaccording to claim 2, wherein a voltage is applied between theelectrodes to emit light.
 4. The electroluminescence device according toclaim 2, wherein a voltage is applied between the electrodes to emitphosphorescence.
 5. A picture display apparatus, comprising anelectroluminescence device according to claim 2, and a means forsupplying electric signals to the electroluminescence device.
 6. A metalcoordination compound represented by the following formula:

wherein CyN1 is a cyclic group having a nitrogen atom and is bonded toIr via the nitrogen atom, and CyC1 is a cyclic group having a carbonatom and is bonded to Ir via the carbon atom and bonded to CyN1 via acovalent bond, at least one of CyN1 and CyC1 having the followingsubstituent

and either or both of CyN1 and CyC1 have an optional substituentselected from halogen, cyano, nitro, trialkylsilyl of which alkyl isindependently a linear or branched alkyl group having 1 to 8 carbons ora linear or branched alkyl group having 1 to 20 carbons of which thealkyl group optionally includes one or non-neighboring two or moremethylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—,—O—CO—, —CH═CH— or C═C— and the alkyl group optionally includes ahydrogen atom that can be optionally replaced with a fluorine atom. 7.An electroluminescence device, comprising: a pair of electrodes disposedon a substrate, and a luminescence unit comprising at least one organiccompound disposed between the electrodes, wherein the organic compoundcomprises a metal coordination compound represented by the formula inclaim
 6. 8. The electroluminescence device according to claim 7, whereina voltage is applied between the electrodes to emit light.
 9. Theelectroluminescence device according to claim 7, wherein a voltage isapplied between the electrodes to emit phosphorescence.
 10. A picturedisplay apparatus, comprising an electroluminescence device according toclaim 7, and a means for supplying electric signals to theelectroluminescence device.